Hair dyeing process and composition containing {60 -cyano-methanesulfonamido-nitrobenzene derivatives

ABSTRACT

Hair dyeing processes and compositions containing Alpha -cyanomethanesulfonamido-nitrobenzene compounds having the formula   where Y represents hydrogen, chlorine, bromine or an alkoxy having 1 to 4 carbon atoms and Z represents NH2 or OH, and wherein the processes of dyeing hair use these compounds directly or in combination with couplers for oxidation dyeing.

United States Patent [191 Saygin 1451 Sept. 30, 1975 [75] Inventor:Ferdi Saygin, Dusseldorf, Germany [73] Assignee: Henkel & CieG.m.b.I-I., Dusseldorf,

Germany [22] Filed: Aug. 16, 1973 [21] Appl. No.: 388,728

[301 Foreign Application Priority Data Aug. 21, 1972 Germany 2241015[52] U.S. C1. 8710.1; 8/10; 8/10.2; 8/11; 8/32; 260/465 E; 424/70 1511Int'. C1. A6lK 7/13 [58] Field of Search 260/465 E; 8/102, 10, 8/101,11, 32; 96/100 [56] References Cited UNITED STATES PATENTS 2,441,4915/1948 Kendall et a1 96/100 X 3,388,148 6/1968 Altman 8/10.] X 3,629,33012/1971 Brody et a1. 8/101 X 3,649,160 3/1972 Kalopissis et a1 8/10..23,702,861 11/1972 Howe .I 260/465 E 3,781,323 12/1973 Wagner ct a1 1.260/465 E Primary Examiner-Albert T. Meyers Assistant ExaminerVera CClarke Attorney, Agent, or FirmHammond & Littell 5 7 ABSTRACT Hairdyeing processes and compositions containinga-cyano-methanesulfonamido-nitrobenzene compounds having the formulawhere Y represents hydrogen, chlorine, bromine or an alkoxy having 1 to4 carbon atoms and Z represents N11 or OH, and wherein the processes ofdyeing hair use these compounds directly or in combination with couplersfor oxidation dyeing.

8 Claims, No Drawings I HAIR DYEING PROCESS AND COMPOSITION CONTAINING va-CYANO-METHANESULFONAMIDO- NITROBENZENE DERIVATIVES wherein Y is amember selected from the group consist- 5 OBJECTS OF THE INVENTION Anobject of the present invention is the develop ment of ana-cyano-methanesulfonamido-nitrobenzene compound having the formulaNH,-SO CH CN wherein Y is a member selected from the group consisting ofhydrogen, chloro, bromo, and alkoxy having 1 to 4 carbon atoms, and Z isa member selected from the group consisting of amino and hydroxyl.

Another object of the invention is the development of an aqueouspreparation for the direct dyeing of human hair consisting essentiallyof 1) from 0.1% to 5% by weight of the abovea-cyano-methanesulfonamido-nitrobenzene compounds; (2) from 0% to 30% byweight of a surfactant; (3) from 0% to 25% by weight of a thickener; and(4) from 40% to 99.9% by weight of water.

A further object of the invention is the development of an aqueouspreparation for the dyeing of human hair consisting essentially of 1)from 0.2% to 5% by weight of an oxidation dyestuff combination. of adeveloper component, and a coupling component in substantially equimolaramounts, said coupling component consisting essentially of the abovewcyano-methanesulfonamido-nitrobenzene compounds; (2) from 0% to 30% byweight of a surfactant; (3) from O to 25% by weight of a thickener; and(4) from 40% to 99.8% by weight of water.

A yet further object of the inventionis the development of a process fordyeing human hair consisting essentially of applyingto said hair attemperatures ranging from about 150 to 40C for a time sufficient toeffect dyeing, an effective amount of either of the above aqueouspreparations.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention provides noveloz-cyanomethanesulfonamido-nitrobenzene compounds having the formulaExamples of compounds of the described type are:.-

2-amino-3-( cx-cy'ano-methanesulfonamido l -nitrobenzene, 1 2-amino-4-(a-cyano-methanesulfonamido 1 -nitrobenzene, 1-amino-4-(a-cyano-methanesulfonamido )-2-nitro benzene,

methanesulfonamido)-3-nitro-benzene, l-amino-5-(a-cyano-m'ethanesulfonamido ).-4-

methoxy-2-nitro-benzene, 2-amino-3-chloro-4-(a-cyanomethanesulfonamido l-nitro-be nzene, 1-amino-3-(a-cyano-methanesulfonamido )-2-nitrobenzene,1-arnino-2-( a-cyano-methanesulfonamido )-4-nitrobenzene, 2-aminola-cyano-methanesulfonamido )-4-nitrobenzene,l-amino-5-brOmo-2-(a-cyanome'thanesulfonamido )-4-nitrO-benzene,l-amino-2-( a-cyano-methanesulfonamido )-3-nitrobenzene, l-amino-3-(oz-cyano-methanesulfonamido )-5-nitrobenzene,l-amino-2-chloro*3-(a-cyanomethanesulfonamido )-5-nitro-benzene,l-amino-2-butOxy-4-(a-cyanomethanesulfonamido )-5-nitro-benzene,4-amino-2-( a-cyano-methanesulfonamido l -nitrobenzene, 2-aminol-ethoxy-4-( a-cyanomethanesulfonamido)-5-nitro-benzene, 2-(a-cyano-memthanesulfonamido )-4-nitro-phenol,2-(a-cyano-methanesulfonamido )-6-nitro-phenol 4-chloro-2-(a-cyano-methanesulfonamido)-6-nitrophenol,2-(oz-cyano-methanesulfonamido )-3-methoxy-6- nitro-phenol, 6-chloro-2-(a-cyano-methanesulfonamido)-4-nitrophenol,2-(a-cyano-methanesulfonamido)-5-nitrO-phenol, 4-bromo-S-(a-cyano-methanesulfonamido )'2-nitrophenol,4-(a-cyano-methanesulfonamido)-2-nit'rophenol, 3-(a-cyano-methanesulfonamido )-2-nitrO-phenol,2-(a-cyano-methanesulfonamido)-5-nitro-phenol,2-(a-cyano-methanesulfonamido)-3-methoxy-5- nitro-phenol,5-chloro-2-(a-cyano-methanesulfonamido)-4-nitrophenol,2-(a-cyano-methanesulfonamido)-3-nitro-phenol,5-butoxy-2-(a-cyano-methanesulfonamido)-3-nitrophenol,3-(oz-cyano-methanesulfonamido)-5-nitro-phenol,

2-bromo-4-( a-cyano-methanesulfonamido )-3-nitrophenol,2-ethoxy-5-(oz-cyano-methanesulfonamido)-4-nitrophenol. The compounds inaccordance with the invention may be produced by reacting thecorresponding nitroamino-phenols or diamino-nitro-benzenes, substitutedif required, wiith the stoichiometric quantity of chlorosulfonylacetonitrile required for the monosubstitution of an amino group.Advantageously, reaction is effected in the presence of a solvent suchas aliphatic hydrocarbons, benzene, chlorobenzene, tetrahydrofuran, insuch a manner that the chlorosulfonyl acetonitrile dissolved in theparticular solvent is added to the nitroamino-phenols ordiamino-nitrobenzenes drop by drop while cooling with ice. After thesaid substances have been added, the reaction mixture is maintained fora few hours at room temperature under agitation and is subsequentlypoured into water and the reaction product, obtained in the form of anoil or in solid form, is separated. Thea-cyano-methanensulfonamidonitrobenzene reaction products can bepurified by recrystallization from ethanol.

The compounds in accordance with the invention are valuable hair dyes.They may be used as direct dyes which produce yellows of various tints.Compared with the starting substances used for their production, whichare known as direct dyestuffs, they are characterized by betterabsorption and fastness properties, and also provide widely differingtints.

Furthermore, the compounds in accordance with the invention can be usedas yellow couplers in oxidation dyes in combination with conventionaldeveloper substances, and the color tints obtainablecan be varied bymeans of the developer components, and the intensity of the oxidationcan be varied through various tints of yellow to brown.

Consequently, a further object of the invention is the use of compoundsof the general formula in which Y represents hydrogen, chlorine,bromine, or an alkoxy group having 1 to 4 carbon atoms, and Z representsan NH or OH-group in preparations for dyeing hair.

In another aspect, therefore, the invention provides an aqueouspreparation for the direct dyeing of human hair consisting essentiallyof (1) from 0.1% to 5% by weight of the abovea-cyano-methanesulfonamidonitrobenzene compounds; (2) from to 30%,preferably 0.5% to 30%, by weight of a surfactant; (3) from 0% to 25%,preferably 0.1% to 25%, by weight of a thickener; and (4) from 40% to99.9%, preferably 40% to 99.3%, by weight of water; as well as anaqueous preparation for the dyeing of human hair consisting essentiallyof l from 0.2% to 5% by weight of an oxidation dyestuff combination of adeveloper component and a coupling component in substantially equimolaramounts, said coupling component consisting essentially of the abovea-cyano-methanesulfonamidonitrobenzene compounds; (2) from 0% to 30%,preferably 0.5% to 30%, by weight of a surfactant; (3) from O to 25%,preferably 0. 1% to 25%, by weight of a thickener; and (4) from 40% to99.8%, preferably 40% to 99.3%, by weight of water.

Either of the above preparations can be used in the process for dyeinghuman hair consisting essentially of applying to said hair attemperatures ranging from about 15 to 40C for a time sufficient toeffect dyeing, an effective amount of either of the above aqueouspreparations.

A particular embodiment of this subject of the invention relates to theuse of compounds of the abovementioned formulas in combination withconventional developer substances in preparation for the oxidativedyeing of hair.

In this instance, suitable developer substances are the compounds whichare normally used for this purpose. The most important examples areprimary aromatic amines having a further functional group in theparaposition, or else a 4-aminopyraz0lone.

Preferred 4-aminopyrazolones are compounds of the generic formulawherein R and R are hydrogen or an organic radical having 1 to 10 carbonatoms.

The organic radical R, can be an alkyl having 1 to 10 carbon atoms, anaryl, such as phenyl, hydroxyphenyl, sulfonylphenyl, sulfonamidophenyl,aminophenyl, lower alkylolphenyl, lower alkylphenyl, loweralkylaminophenyl and di-lower alkylaminophenyl where the alkyls andalkylols have 1 to 4 carbon atoms, or a heterrocyclic radical, such asthe pyridyl. Functional groups may be present, particularly on the aryl,as indicated above, such as OH, NH NHCH N(CH or halogen atoms, i.e.,fluorine, iodine, bromine, and particularly chlorine. Furthermore, thefollowing groups may be present as organic radicals: COOH, COOR', CONHCONHR', CONR'R", wherein R and R are alkyl or hydroxyalkyl having 1 to 4carbon atoms.

The organic radical R can be an alkyl having 1 to 10 carbons, an aryl,such as those mentioned above for R or a heterocyclic radical, such asthe pyridyl. Functional groups may be present. Particularly, hydrocarbonradicals having 1 to 10 carbons are applicable containing as functionalgroups OH, NH COOH, CONH SO H and SO NH As aromatic radical, a phenyl isespecially applicable. It may be substituted with alkyl or hydroxyalkylgroups having 1 to 4 carbons or other substituents, such as halogen,preferably Cl, NH OH, COOH, CONH- CONHR', CONR'R", SO H and SO NH Itfrequently is opportune to employ the 4- aminopyrazolone in the form oftheir water-soluble acid addition salts, such as the hydrochloride,sulfate or oxalate, because the resistance to atmospheric air isincreased.

4- Aminopyrazolones which are suitable as develop- .ers in the processof the invention are as follows:

l-ethyl-4-aminopyrazolone l-n hexyl-4-aminopyrazolonel-n-decyl4-aminopyrazolone l-phenyl-4-arninopyrazolone l-(p-hydroxyphenyl )-4-aminopyrazolone l-(p-sulfonylphenyl)-4-aminopyrazolone 3-methyl-4-aminopyrazolone3-i-propyl-4-aminopyrazolone 3-n-octyl-4-aminopyrazolone3-phenyl-4-aminopyrazolone 3-(p-ethylphenyl)-4-aminopyrazoloneB-(p-aminophenyl )-4-aminopyrazolone3-(p-dimethylaminophenyl)-4-aminopyrazolone 3-( m-chloropheny])-4-aminopyrazolone 3-(4-pyridyl)-4-aminopyrazolone1-methyl-3-phenyl-4-aminopyrazolone l-ethyl-3-(o-hydroxyphenyl)-4-aminopyrazolone l-n-decyl-3-(p-methylaminophenyl)-4- aminopyrazolonel-phenyl-3-n butyl-4-aminopyrazolonel-(p-sulfonamidophenyl)-3-n-octy1-4- aminopyrazolone l-(p-sulfonamidophenyl)-3-phenyl-4- aminopyrazolone l p-ethylphenyl)-3-phenyl-4-aminopyrazolone l-(p-beta-hydroxyethylphenyl )-3-phenyl-4-aminopyrazolone l-(p-hydroxyphenyl )-3-n-octyl-4-aminopyrazolone l-(p-hydroxyphenyl )-3-n-octyl-4-aminopyrazolone 1-( pcarboxyphenyl)-3-n-octyl-4-aminopyrazolone l-( p-carbamidophenyl)-3-n-octyl-4-aminopyrazolone 4-aminopyrazolone-3-carboxylic acid4-aminopyrazolone-3-carboxylic acid-ethyl ester4-aminopyrazolone-3-carboxylic acid-mbutyl ester4-aminopyrazolone-3-carboxylic acid-methylamide4-aminopyrazolone-3-carboxylic acidhydroxymethylamide4-aminopyrazolone-3-carboxylic acid-di-nbutylamideacid-ethyl-betaacid-n- 1-n-butyl-4-aminopyrazolone-3-carboxylicacidmethyl ester l-n-hexyl 4-aminopyrazolone-3-carboxylic acidethylester l-n-heptyl-4-aminopyrazolone-3-carboxylic acidl-n-decyl-4-aminopyrazolone-3-carboxylic acid-di-npropylamidel-n-decyl-4-aminopyrazolone-3-carboxylic beta-hydroxyethyl esterl-phenyl-4-aminopyrazolone-3-carboxylic acidl-phenyl-4-aminopyrazolone-3-carboxylic acid-ethyl esteracidl-phenyl-4-aminopyrazolone-3-carboxylic acid-B- hydroxyethyl ester1-phenyl-4-aminopyrazolone-3-carboxylic acidamide acidacidtional groupin para-position are, e.g., pphenylenediamine, p-toluylenediamine,pdiaminoanisole, p-methylaminoaniline, pethylaminoaniline,p-aminodiphenylamine, pdimethyaminoaniline, p-diethylaminoaniline,p-dibeta-hydroxyethylaminoaniline, p-aminophenol, p-

diaminoanisole, or compounds of the kind named which additionallycontain one or more functional groups such as OH, NR NHR', NR'R, where Rand R" again are lower alkyls or hydroxyalkyls having 1 to 4 carbonatoms.

Preferably, these aromatic biand polyfunctional amines have the formulawherein Y is a member selected from the group consisting of OH, NH NHR',NR'R and NHC l-l and Z is a member selected from the group consisting ofH, R, Y and OR, where again R and R are alkyls or hydroxyalkyls having 1to 4 carbon atoms.

Further suitable developers include diamino pyridine and itsderivatives, for example 2,5-diamino-pyridine, and heterocyclichydrazone derivatives, for example pyridone hydrazones such asl-ethyl-pyridone-Z- hydrazone.

The coupling components according to the invention are suitably used insubstantially equimolar quantities with respect to the developers used.However, it is also possible to employ the coupling component in acertain excess over the stoichiometric amount or in a certain lesserquantity than the stoichiometric amount. Both the coupling componentsand the developers may be mixtures of compounds of the above-mentionedkind.

The oxidative coupling, that is, the development of the dyeing, may alsobe effected according to known procedures such as by the oxygen of theair. However, chemical oxidizing agents are suitably used, especiallyhydrogen peroxide orits adducts with urea, melamine and sodium borate,as well as mixtures of such hydrogen peroxide adducts with potassiumperoxydisulfate.

The compounds according to the invention may be present in the form ofaqueous preparations, such as solutions or emulsions. Such preparationsshould contain the direct'dye or the dyestuffs combination of couplingcomponent and developer component in amounts of from 0.1% to by weight,preferably 0.1% to 2% by weight.

The compounds according to the invention may be applied in the form ofcreams or emulsions. For this purpose the direct dyes, or mixtures ofoxidative dyestuffs combinations of developers and couplers may be mixedwith the ingredients usually present in such preparations. Suchingredients include any anionic or nonionic wetting agents or detergentssuch as for example, alkylbenzenesulfonates, fatty alcohol sulfates,higher alkylsulfonates, higher fatty acid ethanolamides, or ethyleneoxide adducts on higher fatty acids, higher fatty alcohols oralkylphenols. Further, such preparations may contain thickeners, as forexample, methylcellu: lose, starch and also higher fatty alcohols,paraffin oil and fatty acids, as well as perfume oils or hair treatmentagents, for example pantothenic acid and cholesterol,

The additives are utilized in the amounts effective for this purpose. Aneffective amount of a wetting agent or surfactant added is especiallyfrom 0.5% to 30% by weight; and an effective amount of a thickeningagent added is from 0.1% to 25% by weight, calculated in each case onthe total composition. The concentration of the direct dye or thedyestuffs combinations in such cream or emulsion preparations is from0.1% to. 5% by weight preferably 0.2% to 2%, based upon the .totalcomposition, depending on the purpose for which the agent is to be used.The application of the direct dye or dyestuffs combinations may beeffected at temperatures between C and 40C preferably room temperature,in weakly acid, neutral or preferably alkaline medium.

The dyeings obtained have the advantages of a good light fastness, agood washing fastness and a good fastness to rubbing. A specialadvantage of the hair dyes according to the invention is that they maybe used both in direct dyeing and as coupling components in oxidationdyestuffs to obtain yellow colorations.

The following examples are merely illustrative of the 3 presentinvention without being deemedlimitative in any manner thereof.

EXAMPLE 1 a v l-amino-b 2-( a-cyano-methanesulfonamido)-4-nitro-benzene8 Melting point: 185 to 187C Analysis. Molecular Weight calculated for CH N O S.

Calculated: C 37.50%; H 3.12%; N 21.88%. Found: C 37.72%; H 2.86%; N22.07%.

EXAMPLE 2 4-amino-2-( a-eyano-methanesulfonamido l -nitrobenzenecalculated for EXAMPLE 3 1-amino'-4-( a-cyano-methanesulfonamido)-2-nitrobenzene 15.3 gm (0.1 mol) of 1,4-diamino-2-nitro-benzenedissolved in 200 ml of absolute tetrahydrofuran, and 14 gm (0.1 mol) ofchlorosulfonyl acetonitrile dissolved in 50 ml of absolutetetrahydrofuran were reacted in the manner described in Example 1. Thereaction product was recrystallized from ethanol. The precipitatefiltered off was washed with a little ether and was subsequentlyrecrystallized again from water.

Melting point: 157 to 162C. Analysis. Molecular weight C H N O S. I

Calculated: C 37.50%; H 3.12%; N 2l.88%. I Found: C 37.51%; H 2.79%, N22.07%.

calculated for EXAMPLE 4 4-chloro-2-(a-cyano-methanesulfonamido)-6-nitrophenol '1 8.8 gm (0.1 mol) of2-amino-4-chloro-6-nitrophenol suspended in ml of absolutetetrahydrofuran, and 14.0 gm (0.1 mol) of chlorosulfonyl acetonitriledissolved in 50 m1 absolute tetrahydrofuran, were reacted in the samemanner as described in Example 1.

The precipitate was recrystallized twice from ethanol.

Melting point: 174 to 177C Analysis, Molecular weight calculated for'Calculated; C 32.93%; H 2.19%; H 14.41%.

Found: C 33 .5l%; H 2.06%; N 14.53%.

EXAMPLE 5 6-ch'lor'o- 2-("oz-cyano-methanesulfonamido )-4-nitrophenol18.8 gm (0.1 mol) of 2-amino-6-chloro-4-nitrophenol suspended in 100 mlof absolute tetrahydrofuran, and 14.0 gm 0.1 mol) of chlorosulfonylacetonitrile dissolved in 50 ml of absolute tetrahydrofuran, werereacted in the same manner as described in Exam- EXAMPLE 6 calculatedfor 2-( a-cyano-methanesulfonamido )-4-nitro-phenol 15.4 gm (0.1 mol) of2-amino4-nitro-phenol dissolved in 100 ml of absolute tetrahydrofuran,and 14.0 gm (0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 mlof absolute tetrahydrofuran, were reacted in the l 5 EXAMPLE 7 4-(a-cyano-methanesulfonamido)-2-nitro-phenol 15.4 gm 1.0 mol) of4-amino2-nitro-phenol dissolved in 100 ml of absolute tetrahydrofuran,and 14.0 gm (0.1 mol) of chlorosulfonyl acetonitrile dissolved in 50 mlof absolute tetrahydrofuran, were reacted in the same manner asdescribed in Example 1. The precipitate was recrystallized from ethanol.

Melting point: 150 to 155C Analysis. Molecular weight calculated forCHHTNSOSS. 35

Calculated: C 37.36%; H 2.74%; N 16.34%. Found: C 37.71%; H 2.74%; N16.29%.

EXAMPLE 8 2 parts by weight of1-amino-2-(oz-cyano-methanesulfonamido)-4-nitro-benzene wereincorporated in a cream base of the composition:

10 parts by weight of fatty alcohols C to C 10 parts by weight of fattyalcohol sulfate (commercial mixture C to C 75 parts by weight of water.and the pH value of the mixture was adjusted to 9.5 by adding ammonia.This emulsion was made up to 100 parts by weight with water. The dyeingcream thus obtained was applied to human hair which has turned greynaturally, and was allowed to act for 30 minutes at room temperature.The hair was subsequently washed and dried. The result was hair whichhad been dyed a deep yellow color.

EXAMPLES 9 to 14 Using the same procedure as stated in Example 8, butwith the use of the dye components in Examples 2 to calculated for 20 7,listed in the following Table, the hair colors given in the same linewere obtained.

Ex. Hair Color No. Dye component obtained 94-amino-2-(a-cyano-methanesulfonamido)-1-nitro-benzene olive yellow 101-amino-4-( a cyano-methanesulfonamido )-2-nitro-benzene topaz-yellow ll 4-ch1oro-2-(a-cyano-methanesulfonamido )-6-nitro-phenol l26-chloro-2-(a-cyano-methanesulfon pompeian yellow amido)-4-nitro-phenolhoney yellow 1 3 2(a-cyano-methanesulfonamido )-4- nitro-phenol oliveyellow 14 4-(a-cyano-methanesullonamido )-2- nitro-phenol ivory EXAMPLE1 5 Equimolar quantities of 4-amino-1-phenyl-3-carbamoyl-pyazolone-Sacting as a developer component, and1-amino-2-(a-cyano-methanesulfonamido )-4-nitrobenzene acting as acoupler component, were emulsified in a cream base as described inExample 8. The molar concentrations are so calculated that, assuming100% reaction upon the subsequent oxidative coupling reaction, 2 gm ofdye are present in 100 gm of cream (corresponding to a 2% concentrationof dye).

The emulsion was adjusted to a pH value of 9.5 by adding ammonia and wassubsequently made up to 100 parts by weight with water. The dyeing creamthus obtained dyed human hair mustard brown to yellowist brown within 30minutes by virtue of the action of the atmospheric oxygen or a 1% or 9%solution of hydrogen peroxide. The various tints of color were obtainedin accordance with the oxidation. agents used (or their differentconcentrations).

EXAMPLES 16 to 52 Following the same procedure as in Example 15, butwith the use of the developers and couplers given in the following Tableas dye components (a) and (12), human hair which had turned greynaturally was dyed and the colors given in the last column were obtained(with atmospheric oxygen and a 1% and a 9% H 0 solution). The dyecomponents were used in equimolar quantities. The total quantity of thedye to be formed was 2 gm in 100 gm of the cream base in each case, andthe reaction time was 30 minutes at room temperature.

The developer components under a are abbreviated in the Table asfollows:

4-amino-1-phenyl-3-carbamoyl-pyrazolone-5 A4-amino-1-phenyl-3-ethoxycarbonyl-pyrazolone-5 B4-amino-1H-3-ethoxycarbonyl-pyrazolone-5 C p-toluylene diamine Dl-methy1-pyridone-Z-hydrazone E 1-methy1-quinolone-4-hydrazone F Ex- Dyecomponents Tint of the dyed hair ample No. a) develb) coupler By airoxidation 1% H 0 solution 9% H 0 solution o er 16 B l-amino-2-( acyanomethanesulfonamido) -4-nitro-benzene olive brown brass yellowreddish yellow 17 C ditto linoleum brown olive brown toffee brown 18 Dditto olive hrown nut brown hazelnut brown -Continued Ex- Dye componentsTint of the dyed hair ample No. a) develb) coupler By air oxidation 1% Hsolution 9% H 0 solution oper 19 E ditto olive olive 20 F dittoyellowish brown yellowish brown light brown 21 A 4-amino-2-(a-cyanomethanesulfonamido) -l-nitro-benzene olive brown olive olive 22 Bditto olive brown honey yellow blonde 23 C ditto olive brown oliveyellow olive yellow 24 D ditto olive brown dark brown linoleum brown 25E ditto olive yellow olive green olive brown 26 F ditto olive yellowolive brown golden yellow 27 A l-amino-4-(a-cyanomethanesulfonamido)-2-nitro-benzene rust brown cocoa brown Titian red 28 B ditto cinnamonbrown light brown autumn gold 29 C ditto brown cinammon brown autumngold 30 D ditto autumn gold dark brown reddish brown 31 E l-amino-4-(a-cyanomethanesulfonamido) -2-nitro-benzene cognac brown dark brown darkbrown 32 F ditto terra di Siena hazelnut brown dark brown 33 AZ-(a-cyano-methanesulfonamido) -4-chloro-6-nitrophenol somali brown fawncolored Titian red 34 B ditto brick red terra di Siena brownish orange35 C ditto Titian red autumn gold reddish gold 36 D ditto brick redbeaver brown umbra 37 E ditto brick red somali brown dark brown 38 Fditto reddish gold reddish gold autumn gold 39 AZ-(a-cyanomethanesulfonamidoJ--chloro- 4-nitro-phenol bronze brownbronze brown yellowish brown 40 B ditto olive brown olive brown darkyellow 4] C ditto yellowish brown olive brown dark yellow 42 D dittoolive brown rust brown yellowish brown 43 E ditto dark yellow yellow 44A 2-( a-cyano-methanesulfonamido) -4-nitro-phenol olive brown brownbronze brown 45 ditto. khaki khaki greyish yellow 462(a-cyano-methanesulfonamido) -4-nitro-phenol clay colored honey yellowhoney yellow 47 D ditto golden yellow rust brown linoleum brown 48 Fditto ochre yellow auburn 49 A 4-(a-cyano-methanesulfonamido)-2-nitro-phenol greyish brown greyish brown reddish grey 50 D dittonougat brown nutria brown beaver brown 51 E ditto olive brown violetbrown violet brown 52 F ditto Pompeian yellow brown brown groupconsisting of amino and hydroxyl; (2) from 0% The preceding specificembodiments are illustrative to 30% by weight of a surfactant selectedfrom the of the practice of the invention. It is to be understood,

however, that other expedients known to those skilled 45 groupconsisting of an anionic wetting agent and a nonin the art, or disclosedherein, may be employed withionic wetting agent; (3) from 0% to 25% byweight of out departing from the spirit of the invention or the athickener; and (4) from 40% to 99.9% by weight of scope of the appendedclaims. water.

I' claim: 2. The aqueous preparation of claim 1, wherein said 1. Anaqueous preparation for the direct dyeing of 50a-cyano-methanesulfonamido-nitrobenzene compound human hair consistingessentially of (1) from 0.1% to is selected from the group consisting ofl-amino-2-(a- 5% by weight of ana-cyano-methanesulfonamidocyano-methanesulfonamido)-4-nitr0-benzene, 4-nitrobenzene compound having the formulaamino-2-(a-cyano-methanesulfonamido)-l-nitro- 55 benzene, l-amino-4-(a-cyano-methanesulfonamido Z 2-nitro-benzene, 4-chloro-2-(a-cyano-methanesulfonamido )-6-nitro-phenol,6-chloro-2-(a-cyanomethanesulfonamido )-4-nitro-phenol 2-'( a-cyano- YNH SOCH CN methanesulfonamido)-4-nitro-phenol, and 4-(a-cyano Imethanesulfonamido)-2-nitro-phenol.

3. A process for direct dyeing human hair consisting 2 essentially ofapplying to said hair at temperatures ranging from about 15C to 40C fora time sufficient to effect dyeing, an effective amount of the aqueouswherein Y is a member selected from the group consistpreparatons ofclalm ing of hydrogen, chloro, bromo and alkoxy having 1 to 4 carbonatoms, and Z is a member selected from the 4. An aqueous preparation forthe dyeing of human hair consisting essentially of (1) from 0.2% to 5%by weight of an oxidation dyestuff combination of a developer componentand a coupling component in substantially equimolar amounts, saidcoupling component consisting essentially of ana-cyano-methanesulfonamido-nitrobenzene compound having the formulawherein Y is a member selected from the group consisting of hydrogen,chloro, bromo and alkoxy having 1 to 4 carbon atoms, and Z is a memberselected from the group consisting of amino and hydroxyl; (2) from to byweight of a surfactant selected from the group consisting of an anionicwetting agent and a nonionic wetting agent; (3) from O to 25% by weightof a thickener; and (4) from to 99.8% by weight of water.

5. The aqueous preparation of claim 4, wherein saida-cyano-methanesulfonamido-nitrobenzene compound is selected from thegroup consisting of l'-amino-2-(acyano-methanesulfonamido)-4-nitro-benzene, 4 amin- 0-2-(a-cyano-methanesulfonamido 1 -nitro-benzene, l-amino-4-(a-cyano-methanesulfonamido )-2-nitrobenzene,4-chloro-2-(a-cyano-methanesulfonamido)- 6-nitro-phenol,6-chloro-2-(a-cyano-methanesulfonamido)-4-nitro-phenol,Z-(a-cyano-methanesulfonamido)-4-nitro-phenol, and4-(a-cyanomethanesulfonamido)-2-nitro-phenol.

6. The aqueous preparation of claim 4, wherein said developer componentis selected from the group consisting of a 4-amino-pyrazolone, awater-soluble acid addition salt of said 4-amino-pyrazolone, an aromaticamine having at least one primary amino group and another functionalgroup in the para-position, a diaminopyridine and a pyridone hydrazone.

7. The aqueous preparation of claim 4, wherein said developer componentis selected from the group consisting of 4-aminol-phenyl-3-carbamoyl-pyrazolone-54-amino-1-phenyl-3-ethoxycarbonyl-pyrazolone-5, 4-aminolH-3-ethoxycarbonyl-pyrazolone-5, p-toluylene diamine,1-methyl-pyridone-2-hydrazone and lmethyl-quinolone-4-hydrazone.

8. A process for dyeing human hair consisting essentially of applying tosaid hair at temperatures ranging from about 15 to 40C for a timesufficient to effect dyeing, an effective amount of the aqueouspreparation of claim 4.

1. AN AQUOUS PREPARATION FOR THE DIRECT DYEING OF HUMAN HAIR CONSISTINGESSENTIALLY OF (1) FROM 0.1% TO 5% BY WEIGHT OF ANA-CYANO-METHANESULFONAMIDO-NITRONENZENE COMPOUND HAVING THE FORMULA 2.The aqueous preparation of claim 1, wherein said Alpha-cyano-methanesulfonamido-nitrobenzene compound is selected from thegroup consisting of 1-amino-2-( Alpha-cyano-methanesulfonamido)-4-nitro-benzene, 4-amino-2-( Alpha-cyano-methanesulfonamido)-1-nitro-benzene, 1-amino-4-( Alpha-cyano-methanesulfonamido)-2-nitro-benzene, 4-chloro-2-( Alpha-cyano-methanesulfonamido)-6-nitro-phenol, 6-chloro-2-( Alpha-cyano-methanesulfonamido)-4-nitro-phenol, 2-( Alpha-cyano-methanesulfonamido)-4-nitro-phenol, and 4-( Alpha-cyano-methanesulfonamido)-2-nitro-phenol.
 3. A process for directdyeing human hair consisting essentially of applying to said hair attemperatures ranging from about 15*C to 40*C for a time sufficient toeFfect dyeing, an effective amount of the aqueous preparations ofclaim
 1. 4. An aqueous preparation for the dyeing of human hairconsisting essentially of (1) from 0.2% to 5% by weight of an oxidationdyestuff combination of a developer component and a coupling componentin substantially equimolar amounts, said coupling component consistingessentially of an Alpha -cyano-methanesulfonamido-nitrobenzene compoundhaving the formula
 5. The aqueous preparation of claim 4, wherein saidAlpha -cyano-methanesulfonamido-nitrobenzene compound is selected fromthe group consisting of 1-amino-2-( Alpha-cyano-methanesulfonamido)-4-nitro-benzene, 4 amino-2-( Alpha-cyano-methanesulfonamido)-1-nitro-benzene, 1-amino-4-( Alpha-cyano-methanesulfonamido)-2-nitro-benzene, 4-chloro-2-( Alpha-cyano-methanesulfonamido)-6-nitro-phenol, 6-chloro-2-( Alpha-cyano-methanesulfonamido)-4-nitro-phenol, 2-( Alpha-cyano-methanesulfonamido)-4-nitro-phenol, and 4-( Alpha-cyano-methanesulfonamido)-2-nitro-phenol.
 6. The aqueous preparation ofclaim 4, wherein said developer component is selected from the groupconsisting of a 4-amino-pyrazolone, a water-soluble acid addition saltof said 4-amino-pyrazolone, an aromatic amine having at least oneprimary amino group and another functional group in the para-position, adiamino-pyridine and a pyridone hydrazone.
 7. The aqueous preparation ofclaim 4, wherein said developer component is selected from the groupconsisting of 4-amino-1-phenyl-3-carbamoyl-pyrazolone-5,4-amino-1-phenyl-3-ethoxycarbonyl-pyrazolone-5,4-amino-1H-3-ethoxycarbonyl-pyrazolone-5, p-toluylene diamine,1-methyl-pyridone-2-hydrazone and 1-methyl-quinolone-4-hydrazone.
 8. Aprocess for dyeing human hair consisting essentially of applying to saidhair at temperatures ranging from about 15* to 40*C for a timesufficient to effect dyeing, an effective amount of the aqueouspreparation of claim 4.